Aqueous preparations of salts of n, n-disubstituted acid amides of di- or tricarboxylc acids



United States Patent 3,329,608 AQUEOUS PREPARATIONS 0F SALTS 0F N,N-DI-SUBSTITUTED ACID AMIDES OF DI- 0R TRI- CARBOXYLIC ACIDS Armin Hiestand,Binningen, Switzerland, assignor to Ciba Limited, Basel, Switzerland, aSwiss company No Drawing. Filed Apr. 6, 1964, Ser. No. 357,733 Claimspriority, application Switzerland, Apr. 23, 1963,

5,058/ 63 2 Claims. (Cl. 252-8.8)

Aqueous solutions, dispersions and pastes of alkali metal salts of N,N-disubstituted acid amides derived from dicarboxylic acids, such asadipic or sebacic acid, are known. The products are semi-amides, inwhich one carboxyl group takes the form of'a salt and the other containsthe amide grouping formed by reaction with a sec ondary amine. It hasalso been proposed to use aqueous preparations of these semi-amides astextile assistants, for example as softeners (c.f. U.S. Specification2,936,251 granted May 10, 1960 to Bertram J. Garceau et al.) The use ofthese aqueous preparations entails considerable difliculties because thesolutions and dispersions, especially when manufactured with hard water,are unstable and form precipitates after a short time. It has now beenfound that stable solutions and dispersions are obtained even with hardwater when selected assistants are added, and that with the use of thesepreparations the desired improving effects can be obtained on textilematerials. It has now been found that cationic and anionic assistantsare unsuitable and that from the large range of nonionic assistants onlyadducts of ethylene oxide with alkalphenol can be successfully used.When ethylene adducts from higher aliphatic or cycloaliphatic alcohols,from higher fatty acids or higher fatty amines are used, there are infact obtained stable solutions or dispersions of the salts of thesemiamides but the desired improving efiect, especially in themanufacture of softened textile fibers, does not materialise.

The present invention provides aqueous preparations in the form ofsolutions, dispersions or pastes of salts of N,N-disubsti-tuted acidamides of dicarboxylic or tricarboxylic acids, containing in additionper mol of the acid amide salt 0.02 to 0.4 mol of a condensation productfrom 5 to 80 mols of ethylene oxide with 1 mol of an alkylphenol. Theserni-amides correspond preferably to the general formula where Arepresents an aliphatic, cycloaliphatic or aromatic divalent ortrivalent hydrocarbon radical containing at most 8, preferably 2 to 6,carbon atoms; M represents an alkali metal atom; R and R' eachrepresents an oxalic, succinic, malonic, adipic, sebacic, maleic,phthalic,.

tetrahydrophthalic, hexahydrophthalic, terephthalic and 3,329,608-Patentecl July 4, 1967 trimellitic acid and the correspondinganhydrides. The semiamides are obtained by condensing 1 mol of adicarboxylic acid, or of a dicarboxylic acid anhydride, with 1 mol of asecondary amine, for example with 1 mol of a dialkylarnine of theformula RNHRR", or of a monoamideomonoalkylamine of the formula where Ris an aliphatic hydrocarbon radical containing 11 to 2-3 carbon atomsand R represents a divalent radical with 2 to 3 carbon atoms. R" is, forexample, C H 12 25, 15 31 n sa it as 21 43 Rm is CH CH CH CH CH CHg-(|3Hor CH CH-CH2 CH3 H In this case of trimellitic acid or of its anhydride2 mols of secondary amine are used.

A preferred dicarboxylic acid is phthalic acid or its anhydride.Especially suitable secondary amines are N,N- dialkylmonoamines whosealkyl radicals contain 12 to 22 carbon atoms, and condensation productsof 2 mols of a higher fatty acid with 1 mol of diethylenetriamine ordipropylenetriamine. The sodium and potassium salts are the preferredsalts of the semi-amides; advantageously, they are prepared by treatingthe semi-amides with alcoholic sodium or potassium hydroxide solution.

The phenols suitable for the manufacture of the hydroxyethylatedalkylphenols corresponds preferably to the general formula OH l where Xrepresents a straight or branched alkyl or cycloalkyl radical containing1 to 12 carbon atoms and s=1, 2 or 3. Advantageously, at least oneradical X contains 4 to 12 carbon atoms. As relevant examples there maybe mentioned: 'Ilertiary octylphenol, di-tertiary butyl-paracresol,para-tertiary-butyl-ortho-cresol, nonylphenol, dodecyphenol andpara-cyclohexylphenol.

' The nonionic assistant to be used according to .the invention isobtained by adding 5 to 80, preferably 8 to 30, mols of ethylene oxideon to 1 mol of alkylphenol. The amount of ethylene oxide adduct,referred to the salt ofthe semi-amide, cannot be selected at will. Toensure that, on the one hand, a stable aqueous preparation is formedand, on the other hand, material treated with such a preparation isimproved in the desired manner, there must be used 0.02 to 0.4 mol,preferably 0.1 to 0.2 mol of the ethylene oxide condensation product permol of the salt of the semi-amide. The term aqueous preparation coversnot only solutions and dispersions but also pastes. The pastes contain30 to percent'byweight of the mixture of semi-amide and nonionicassistant. Thesolutions and dispersions contain as a rule per liter 0.1to 10 g., preferably 0.2 to

3 g., of the-salt of the semi-amide as well as the nonionic assistant inan amount as statedabove. The mixture of semi-amide and assistant mayalso form a powder from which the desired solution or dispersion isprepared before use. The dry mixture is preferably obtained byspray-drying the aqueous solutions. The

pulverulent preparation is very stable and forms on addition of waterthe said solutions, despersions or pastes.

The combination according to the invention of an alkali metal salt ofthe semi-amide and the hydroxyethylated alkylphenol is distinguishedprimarily by the fact that it is suitable for manufacturing stableaqueous preparations even with hard water, that is to say water having ahardness of 15 to 20 German hardness degrees. These combinations producean excellent soft handle on textile materials. The preparations madewith hard water form as a rule slightly opalescent solutions ordispersions. They are primarily used as agents imparting a soft handleto textile materials in the form of woven fabric, flocks or fibers.Textile materials suitable for such improvement may be natural,regenerated, modified or fully synthetic materials, for example thosefrom cotton, wool, viscose, cellulose-2 /2-acetate, triacetate,polyamides, polyesters and polyacrylonitrile. Furthermore, thepreparations of the invention or aqueous forms thereof are suitable aslevelling agents, as brightening agents, as after-treating agents and asantistatic dressings for textiles, and also as assistants for the paperand leather industries.

It is another advantage of the aqueous preparations that they can beused in conjunction with dyestulfs or water-soluble condensationproducts of urea or melamine with formaldehyde. Undyed textile materialsdo not turn yellow when treated with the combination of the invention.When the solutions of dispersions are caused to circulate vigorously,for example being pumped in circulation apparatus, the products are notprecipitated.

The semi-amides used in the examples are prepared as follows:

Preparation A.-260 g. (0.5 mol.) of a secondary higher dialkylamine and48 g. (0.25 mol.) of trimellitic anhydride are melted at 110 C. andheated at 160 C. under nitrogen until almost 5 g. (abt. 0.25 mol.) ofwater have been eliminated. There are obtained 302 g. (0.25 mol.) of awaxy substance which has an acid number of about 46 and gives anopalescent solution in hot sodium hydroxide solution. The condensationproduct probably corresponds to the formula where R represents a higheralkyl radical containing 16 to 20 carbon atoms.

Instead of the above dialkylamine there may be used other secondaryamines to give the following preparations (l30--C11H as CHzClIz-N-CHzCHit-NH C O-C 171135 In every case a hard, waxy substance is obtainedwhich gives an opalescent solution in hot 10% sodium hydroxide solution.

Preparation B.305 g. (0.5 mol.) of a basic reaction product from 1 mol.of diethylenetriamine and 2 mols. of commercial stearic acid (molecularweight 270) are melted, and 74 g. (0.5 mol.) of powdered phthalicanhydride are added at 90 to 100 C. The mixture is slowly heated undernitrogen to about 160 C.; at 120 to 130 C. a clearly visible exothermicreaction takes place. After cooling, there are obtained 375 g. of abrittle, waxy product of beige color which melts at 58 to 60 C. Thiswaxy substance gives an opalescent solution in 10% sodium hydroxidesolution. The condensation product corresponds to the formulaPreparation C.This product is made as described for preparation B,except that the basic reaction product is replaced by 315 g. (0.5 mol.)of a product prepared in similar manner from oleic acid, or 405 g. (0.5mol.) of a reaction product from 1 mol. of triethylenetetramine with 3mols. of stearic acid.

Preparation D.This product is prepared as described for Preparation B,except that 0.5 mol of phthalic anhydride is replaced by 76 g. (0.5 mol)of tetrahydrophthalic anhydride, to yield 380 g. of a light-colored,brittle wax which gives an opalescent solution in hot 10% sodiumhydroxide solution. An identical product is obtained by using 77 g. (0.5mol) of hexahydrophthalic acid.

Preparation E.--305 g. (0.5 mol) of a basic reaction product from 1 molof diethylenetriamine and 2 mols of commercial stearic acid (molecularweight 270) are melted, and 83 g. (0.5 mol) of terephthalic acid areadded at to C. The mixture is slowly heated under nitrogen to about 200C. After cooling, a hard, waxy substance of light color is obtainedwhich gives an opalescent solution in 10% .sodium hydroxide solution.

Preparation F .-The product is prepared as described for Preparation E,except that 0.5 mol of terephthalic acid is replaced by 73 g. (0.5 mol)of adipic acid, to yield a waxy substance of light-beige color whichgives an opalescent solution in hot 10% sodium hydroxide solution. Asimilar product is obtained by using 101 g. of sebacic acid.

Preparation G.-The product is prepared as described for Preparation B,except that phthalic anhydride is replaced by 59 g. (0.5 mol) ofsuccinic anhydride. The resulting pale-yellow, hard, waxy substanceobtained gives an opalescent solution in hot 10% sodium hydroxidesolution.

Preparation H .The product is prepared as described for Preparation B,except that there are used 260 g. (0.5 mol) of a basic condensationproduct from 1 mol of diethylenetriamine and 2 mols of myristic acid.

Preparation ].The product is prepared as described for Preparation B,except that there are used 370 g. (0.5 mol) of a basic condensationproduct from 104 g. (1 mol) of diethylenetriamine and 68 g. (2 mols) ofbehenic acid.

Preparation K.The product is prepared as described fro Preparation B,except that there are used 316 g. (0.5 mol) of a basic condensationproduct from 132 g. (1 mol) of di-propylenetriamine and 544 g. (2 mols)of commercial stearic acid of molecular weight 270.

Preparation L.The product is prepared as described for Preparation B,except that there are used 310 g. (0.5 mol) of a basic condensationproduct from 370 g. (about 1 mol) of an aminopropyl-alkylamine, obtainedfrom soybean fatty acid by a known method, and 270* g. (1 mol) of astearic acid of molecular weight 270. The condensation productcorresponds to the formula where R represents the radical of soybeanfatty acid.

Pastes of 50% strength are prepared from each of the waxy preparations Ato L in the following manner: 1 mol of the condensation product isstrongly refluxed for 2 hours in 300 g. of alcohol with 1.05 mol ofsodium hydroxide (used in the form of an aqueous solution of strength).The solvent is then evaporated and by heating with water a 50% solutionis prepared which on cooling turns liquid to viscid.

Pastes can alternatively be prepared by boiling 1 mol of the waxypreparation with 1.05 to 1.1 mol of NaOh in sufiicient water to form,when hot, a 50% solution.

EXAMPLE 2 In the following experiments the symbols have the followingmeanings:

=-No soft handle +Trace of soft handle Distinct soft handle +++-Goodsoft handle ++++Very good soft handle s-Smeary soft handle (a) Dippingmethod-The preparation is a 50% paste Preparation, Cotton Viscose N ylonPolyacrylonitrile g.lliter (b) Padding method.Preparation and waterhardness as under (a) above. The material is passed twice through aBenteler padder. Drying is carried out at 70 C.

Cotton Polyacrylonitrile Preparation, Viscose Nylon gJliter Soft watergoods-to-liquor is 1:40. The treatment is carried out for 1 hour each at90 C. with soft water and hard water.

OH; I v

C=O Y 1103s so.n

. I orange (3H3 OH; H0 8 NIH-(3 -NHCOCH O N: N=N

' claret violet blue S 0 H Soft handle 3. 6%

claret violet blue orange Hardwater Polyester Cellulose- 2 g 'acetateF=weight increase in percent.

(c) Exhaustion method-Preparation and water hardness as under (a) above.Goods-t-o-liquor ratio 1 30. The material is immersed in the bath at C.and treated for 30 minutes at room temperature, then centrifuged anddried at 70 C.

Triacetate Celluloseacetate Preparation 1 Cotton Viscose EXAMPLE 3Viscose yarn is treated by the dipping method described in Example 2,except that the preparation used consists of a mixture of the paste ofthe sodium salt of preparation D and an amount, corresponding to 8 molpercent, of the adduct from 30 mols of ethylene oxide with 1 mol ofdodecylphenol.

The viscose hank treated in this manner has a good, soft handle.

EXAMPLE 4 Viscose, cotton, acetate rayon and triacetate rayon yarns aretreated by the exhaustion method described in Example 2, except that thepreparation used consists of a mixture of an amount, corresponding to 8mol percent, of the adduct from 8 mol percent of ethylene oxide with 1mol of tertiary octylphenol and of a paste of 50% strength of the sodiumsalt of preparations A, E, F, G, H, K and L 7 respectively. The treatedyarns display a soft handle which can be improved by rendering thealkaline impregnating liquor slightly alkaline with a small amount offormic acid.

What is claimed is: 1. A composition for improving textile materialsconsisting essentially of a mixture of (1) a salt of anN,N-disubstituted acid amide of a polycarboxylic acid selected from theclass consisting of an aliphatic hydrocarbon dicarboxylic acidcontaining 2 to carbon atoms, phthalic, terephthalic, trimellitic,tetrahydrophthalic and hexahydrophthalic acid, the -N,N-disubstitutedamide grouping having the formula of ethylene oxide with 1 mol of analkylphenol of the general formula '8 where X represents an alkylradical containing 1 to 12 carbon atoms and s is a whole number from 1to 3, which condensation product is present in an amount of 0.02 to 0.4mol per mol of said salt of the acid amide. 2. A composition forimproving textile materials consisting essentially of a mixture of (1) asalt of a half amide of the formula wherein R represents an aliphatichydrocarbon containing 11 to 23 carbon atoms, and of (2) thecondensation prodduct from 8 to 10 mols of ethylene oxide with 1 mol ofnonylphenol, which condensation product is present in an amount of 0.02to 0.4 mol per mol of said salt of the half amide.

References Cited UNITED STATES PATENTS 2,936,251 5/1960 Garceau et al.117-l39.5 2,953,526 9/1960 Bergman et al. 2S2--8.8 2,958,665 11/1960Stefcik et al 252-83 X 3,131,147 4/ 1964 Hiestand et al. 252-8.8

LEON D. ROSDOL, Primary Examiner.

JULIUS GREENWALD, I. T. FEDIGAN,

Assistant Examiners.

1. A COMPOSITION FOR IMPROVING TEXTILE MATERIALS CONSISTING ESSENTIALLYOF A MIXTURE OF (1) A SALT OF AN N, N-DISUBSTITUTED ACID AMIDE OF APOLYCARBOXYLIC ACID SELECTED FROM THE CLASS CONSISTING OF AN ALIPHATICHYDROCARBON DICARBOXYLIC ACID CONTAINING 2 TO 10 CARBON ATOMS, PHTHALIC,TEREPHTHALIC, TRIMELLITIC, TETRAHYDROPHTHALIC AND HEXAHYDROPHTHALICACID, THE N, N-DISUBSTITUTED AMIDE GROUPING HAVING THE FORMULA